CN1930249A - Silanised silicas - Google Patents

Silanised silicas Download PDF

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Publication number
CN1930249A
CN1930249A CNA2005800070906A CN200580007090A CN1930249A CN 1930249 A CN1930249 A CN 1930249A CN A2005800070906 A CNA2005800070906 A CN A2005800070906A CN 200580007090 A CN200580007090 A CN 200580007090A CN 1930249 A CN1930249 A CN 1930249A
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Prior art keywords
structurally
silica
modified
silanization
modified silica
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于尔根·迈尔
马里奥·肖尔茨
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Evonik Operations GmbH
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Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating

Abstract

Silanised, structurally modified silicas, characterised by vinyl groups or vinyl silyl groups fixed to the surface, hydrophobic groups such as trimethyl silyl and/or dimethyl silyl and/or monomethyl silyl additionally being fixed to the surface, having the following physico-chemical properties: BET surface area m<2>/g: 25 - 400 Average primary particle size nm: 5 - 50 pH: 3-10 Carbon content %: 0.1-10 DBP value %: < 200 or not determinable are produced by treating silica with a surface-modifying agent, heat treating and then structurally modifying the mixture obtained. The silica can be used as a filler in silicone rubber.

Description

The silica of silanization
The present invention relates to structurally-modified silica, the Its Preparation Method And Use of silanization.
The invention provides the structurally-modified silica of silanization, it is characterized in that being fixed with in its surface vinyl or vinyl silyl, and also additional fastening has the hydrophobic grouping of trimethyl silyl for example and/or dimetylsilyl and/or monomethyl silyl in its surface, and described structurally-modified silica has following physicochemical property:
BET surface-area m 2/ g:25-400
Average primary particle particle diameter nm:5-50
pH： 3-10
Carbon content %:0.1-10
DBP value %:＜200 or detect less than.
The present invention also provides the method for the structurally-modified silica for preparing described silanization, it is characterized in that handling silica with surface-modifying agent, and thermal treatment is the mixture of modification gained structurally then.
Optionally method is a kind of method of the structurally-modified silica according to preparation silanization of the present invention, it is characterized in that at first water sprays described silica with surface-modifying agent then, remix randomly, thermal treatment and carry out structurally-modified more then.
Can use the used water of acid (for example hydrochloric acid) acidifying, thereby obtain the pH of 7-1.If use kinds of surface properties-correcting agent, they can use together, once use a kind of individually or use as mixture.Surface-modifying agent can be dissolved in the appropriate solvent.After finishing spray, can continue again to mix 5-30 minute.
Then, thermally treated mixture 0.1-6 hour time under 20-400 ℃ temperature.Can heat-treat as under the nitrogen for instance at protective gas.
Another optional method is the method according to the structurally-modified silica of preparation silanization of the present invention, it is characterized in that handling silica with the surface-modifying agent of steam form, and thermal treatment is the mixture of modification gained structurally then.
Can handle silica by surface-modifying agent, under 50-800 ℃ temperature, implement the optional method of silica surface modification then in thermally treated mixture 0.1-6 hour with the steam form.Can heat-treat as under the nitrogen for instance at protective gas.
Can also in the several stages under the differing temps, heat-treat.
Can come application surface properties-correcting agent with single fluid nozzle, two-fluid spray nozzle or ultrasonic nozzle.
Can in heatable mixing tank with spray thrower and moisture eliminator, carry out surface modification continuously or off and on.For instance, proper device can be ploughshare mixing tank, plate dryer, fluidized-bed or flash dryer.
Then, the silica that so prepares by power operation is structurally-modified.Can after structurally-modified, carry out the back grinding.Other conditioning (conditioning) can randomly be carried out after grind structurally-modified and/or back.
For instance, can use ball milling or continous way ball milling to carry out structurally-modified.
For instance, can use jet mill, toothed disk mill or pin mill to carry out the back grinds.
Can perhaps for example nurse one's health continuously or thermal treatment in the fluidized-bed in loft drier for example in batches.Can for example nurse one's health under the protection of nitrogen gas gas.
Can use the silica of pyrolysis preparation, preferably pass through the transpirable silicon compound of flame hydrolysis (for instance as SiCl 4) and the silica of pyrolysis preparation.About this fumed silica (pyrogenicsilica), for example referring to Ullmanns Enzyklop  die der technischen Chemie, the 4th edition, the 21st volume, the 464th page, (nineteen eighty-two).
For instance, can use following material as silica:
Table 1
AEROSIL TT 600 AEROSIL 90 AEROSIL 130 AEROSIL 150 AEROSIL 200 AEROSIL 300 AEROSIL 380 AEROSIL OX50
The CAS number of registration 112945-52-5 (old number: 7631-86-9)
Reaction to water Hydrophilic
Outward appearance Loose white powder
BET 1) surface-area m 2/g 200±50 90±15 130±25 150±15 200±25 300±30 380±30 50±15
Average primary particle diameter mm 40 20 16 14 12 7 7 40
Compacted volume density 2) standard product g/l compacting product g/l (additive " V ") About 60- About 80- About 50 about 120 About 50 about 120 About 50 about 120 About 50 about 120 About 50 about 120 About 130-
Drying loss 3) (105 ℃ of following 2h) when % leaves supply ＜2.5 ＜1.0 ＜1.5 ＜0.5 9) ＜1.5 ＜1.5 ＜2.0 ＜1.5
Combustion loss 4)7)(1000 ℃ of following 2h) % ＜2.5 ＜1 ＜1 ＜1 ＜1 ＜2 ＜2.5 ＜1
pH 5) (in 4% aqueous dispersions) 3.6-4.5 3.7-4.7 3.7-4.7 3.7-4.7 3.7-4.7 3.7-4.7 3.7-4.7 3.6-4.3
SiO 2 8)％ ＞99.8 ＞99.8 ＞99.8 ＞99.8 ＞99.8 ＞99.8 ＞99.8 ＞99.8
Al 2O 33 8)％ ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.08
Fe 2O 3 8)％ ＜0.003 ＜0.003 ＜0.003 ＜0.003 ＜0.003 ＜0.003 ＜0.003 ＜0.01
TiO 2 8)％ ＜0.03 ＜0.03 ＜0.03 ＜0.03 ＜0.03 ＜0.03 ＜0.03 ＜0.03
HCl 8)10)％ ＜0.025 ＜0.025 ＜0.025 ＜0.025 ＜0.025 ＜0.025 ＜0.025 ＜0.025
Retain material on the sieve 6)(according to Mocker, 45 μ m) % ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 0.2
1) with reference to DIN 66,131 2) with reference to DIN ISO 787/XI, JIS K 5101/18 (not sieved)
3) with reference to DIN ISO 787/II, ASTM D 280, JIS K 5,101,/21 4) with reference to DIN 55921, ASTM D 1208, JIS K 5101/23
5) with reference to DIN ISO 787/IX, ASTM D 1208, JIS K 5,101,/24 6) with reference to DIN ISO 787/XVIII, JIS K 5101/20
7) based on 2 hours material 8 of drying under 105 ℃) based on the material of annealing 2 hours down at 1000 ℃
9) special hydrofuge packing 10) HCl content in the combustion loss component
All compounds that are suitable on silica surface fixing vinyl or vinyl silyl and trimethyl silyl and/or dimetylsilyl and/or monomethyl silyl can be used as surface-modifying agent.Preferably can pass through a kind of compound herein, for example 1,3-divinyl-1,1,3,3-tetramethyl-disilazane or dimethyl vinyl silanol are perhaps by multiple compound, for example vinyltriethoxysilane and hexamethyldisilazane or trimethyl silyl alcohol provide vinyl silyl and methyl-silicane base on silica.
Structurally-modified silica according to silanization of the present invention can be as the filler in the silicon rubber.
If the fumed silica of this low structurizing (low-structured) is incorporated in the silicon rubber, can in silicon rubber, obtain brand-new character.
Structural modification has changed the pattern of fumed silica, thereby obtains lower symbiosis degree, and therefore obtains the structure (lower structure) of even lower level.
Silicon rubber can be liquid silastic (LSR).
, molecular weight polydimethylsiloxane between 400,000 and 600,000 between preparation, that have corresponding end group by the conditioning agent that adds hexamethyldisiloxane for example or divinyl tetramethyl disiloxane can be used for elastomerics and use.In order to improve sulfidation and anti tear is propagated, can be by to reaction mixture (VMQ) in, adding the vinyl dimethyl dichlorosilane (DMCS), and in main chain in conjunction with (＜1%) on a small quantity as substituent vinyl.
Except mean chain length shortens 6 times, so viscosity reduces outside 1000 times (20-40Pas), and the molecular structure of liquid silastic (LSR) is identical with HTV almost.Two kinds of components (A and B) of supply equivalent in the treater that has comprised filler, vulcanizing agent and optional other additive.
Two kinds of fillers are arranged: enhancement type filler and non-enhancement type filler.
Being characterized as a little less than the interaction extremely with siloxane polymer of non-enhancement type filler.They comprise chalk, silica powder, diatomite, mica, kaolin, Al (OH) 3And Fe 2O 3The magnitude of particle diameter is 0.1 μ m.They are used for not increasing the viscosity of compound and the Young's modulus of increase Shore hardness and vulcanized rubber in the sulfided state.In the situation of surface treated filler, can also realize the improvement of tear strength.
The enhancement type filler mainly is surface-area＞125m 2The fine particle silica of/g.Reinforcing effect can be owing to the bonding between filler and the siloxane polymer.By with siloxane chain in the hydrogen bridge band of oxygen, the silanol group (3-4.5SiOH group/nm at the silica surface place 2) and the a-alpha, omega-dihydroxy polydimethyl siloxane in the silanol group between form described key.These filler-interpolymer interactions cause the viscosity that increases and have changed second-order transition temperature and crystallization behavior.On the other hand, the polyalcohol-filling material key has improved mechanical characteristic, but also causes the premature hardening (crape sclerosis (crepe hardening)) of rubber.
Talcum is in the mid-way between enhancement type and the non-enhancement type filler.Filler also can be used for producing special-effect.They comprise ferric oxide, titanium dioxide, zirconium white or the barium zirconate that increases thermostability.
Silicon rubber can also comprise catalyzer, linking agent, tinting pigment, antisticking agent, softening agent and coupling agent as annexing ingredient.
In particular for obtaining low Young's modulus, need softening agent.Inner coupling agent is based on function silane, and this function silane can at first interact with base material and interact with crosslinked siloxane polymer (mainly using in RTV-1 rubber) subsequently.
Low-molecular-weight or be rich in compound (monomericsilanol-rich compounds) (diphenyl silanodiol for example, the H of monomer silanol 2O) suppressed premature hardening.They are by having stoped the strong excessively interaction of silanol group in siloxane polymer and the filler in advance with the filler faster response.Also can obtain corresponding effect by partly apply filler (using the filler of methyl-monosilane to handle) with trimethyl silyl.
Can also chemical modification siloxane polymer (phenyl polymer, boron-containing polymer) or mix with organic polymer (butadiene-styrene copolymer).
The low viscosity of stock polymer need strong especially combination and kneading in the mixing device of special exploitation, to realize uniform distribution.Absorb and prevent the crape sclerosis for the ease of filler, during mixing process, use hexamethyldisilazane (HMDS) to make the complete hydrophobization of silica in situ usually.
Implement the sulfuration of LSR mixture by hydrosilication, i.e. addition methyl hydrogen siloxane (having 3 SiH groups in the molecule at least) on the vinyl in polymkeric substance under the catalysis of the Pt of ppm (O) title complex, linking agent and catalyst pack are contained in the independent component when carrying.Special inhibitor (for example 1-ethynyl-1-hexalin) has prevented from scorching takes place when component is mixed, and has at room temperature obtained about 3 days Drain time (droppingtime).Can in very wide scope, regulate proper proportion by the concentration of platinum and inhibitor.
LSR blend glue (LSR blends) is used to prepare the conductive silicon rubber product more and more, because it addition-crosslinkedly can not destroyed by furnace black as the employed peroxide cure of traditional HTV (in HTV blend glue preferred use acetylene black).The furnace black of conduction is also than graphite or metal powder (wherein silver is preferred) easier combination and distribution.
Silicon rubber according to the present invention demonstrates following advantage:
Experiment among the LSR (liquid silastic) shows, compares with hydrophobic educt (educt) (fumed silica), demonstrates significantly lower viscosity according to the structurally-modified hydrophobic oxide compound of embodiments of the invention 1-3 in liquid silicon.
Use does not demonstrate yield-point according to the LSRs of silica preparation of the present invention, because very good flow characteristics is preferred when Working liquids silicon rubber, so this is particularly advantageous.
In addition, embodiment 3 also shows and uses described silica structurally-modified, that vinyl silane is handled can realize the significantly higher propagated advantage of anti tear.
By the oxide compound of utilization structure modification, can use the material that demonstrates extremely low viscosity He no yield-point because of its low structure according to the present invention, and therefore during preparation will not be exposed under the high shear force by described material.Saving energy, time and materials cost, is favourable in conjunction with the preparation of the vulcanized rubber with excellent mechanical properties for the user.
Embodiment
Fumed silica is placed in the mixing tank, and water at first, then with the mixture spray of surface-modifying agent or surface-modifying agent.Then, reaction mixture experience single hop or multistage thermal treatment.With ball milling the material through conditioning is carried out structurally-modified, then if desired with grinding behind the toothed disk mill.If desired, make material structurally-modified or structurally-modified and that grind the back further accept thermal treatment.
Table 2: the preparation general introduction (embodiment) of silica used according to the invention
Title The silica that uses Water content (umber/100 part silica) SM *) (umber/100 part silica) Heat treatment stages 1 temperature [℃]/time length [h] Heat treatment stages 2 temperature [℃]/time length [h] Grind the back **) Thermal treatment ***) temperature [℃]/time length [h]
Sil 1 AEROSIL 200 5 A/5 D/5 140/2 - Not Not
Sil 2 AEROSIL 300 5 B/15 C/1.8 20/2 140/2 Be Be
Sil 3 AEROSIL 300 5 A/8.5 B/20 50/5 140/1 Be 120/2
Sil 4 AEROSIL 300 5 A/16 B/12 20/6 120/5 Be 120/3
Sil 5 AEROSIL 150 5 C/20 130/2 - Be 120/2
Sil 6 AEROSIL 130 2 C/5 D/5 150/3 - Not Not
Sil 7 AEROSIL 300 5 A/8.5 B/20 50/5 140/1 Not Not
Sil 8 AEROSIL 200 5 B/10 C/5 20/20 140/3 Be Not
Sil 9 AEROSIL 300 5 C/16 20/2 140/2 Be Not
Sil 10 AEROSIL 200 2 A/10 B/5 20/2 140/24 Be 120/2
Sil 11 AEROSIL 300 5 A/8.5 B/20 50/5 140/1 Be Not
*) the SM=surface-modifying agent:
The A=vinyltriethoxysilane
The B=hexamethyldisilazane
C=1,3-divinyl-1,1,3,3-tetramethyl-disilazane
The D=methyltrimethoxy silane
Under the situation of using more than one SM, use mixture.
*) back grinding=grind in structurally-modified back
* *) thermal treatment=grind postheat treatment in the back
The relatively preparation of silica
2 kilograms AEROSIL  is placed in the mixing tank, and at blended simultaneously, at first uses 0.1 kg water, the mixture with 0.4 kilogram of hexamethyldisilazane and 0.17 kg ethylene ethyl triethoxy silicane alkane sprays then.After spray is finished, continue to mix again 15 minutes, and at first 50 ℃ of following conditioning reaction mixtures 5 hours, then 140 ℃ of conditionings 1 hour down.
Table 3: according to the physicochemical property of silica of the present invention (embodiment) and comparison silica
Title Compacted volume density [g/l] Drying loss [%] Combustion loss [%] pH C content [%] DBP adsorbs [%] BET specific surface area [m 2/g]
Compare silica 48 0.9 4.1 9.0 4.0 n.d. 197
Sil 1 236 1.2 1.6 4.4 1.1 9.7 136
Sil 2 147 0.7 3.8 6.2 3.8 n.d. 201
Sil 3 120 0.4 3.6 7.5 4.0 n.d. 191
Sil 4 132 0.5 3.0 5.2 3.5 128 189
Sil 5 138 0.2 2.8 5.5 2.8 n.d. 103
Sil 6 249 0.8 1.1 6.3 1.5 91 79
Sil 7 266 1.1 3.4 8.5 4.0 121 204
Sil 8 161 0.9 2.7 6.1 4.3 91 117
Sil 9 132 1.0 4.0 6.7 4.9 n.d. 205
Sil 10 149 0.6 2.8 5.1 2.8 n.d. 155
Sil 11 163 0.8 3.5 8.5 4.0 n.d. 197
The fumed silica of test structure modification in silicon rubber
Product in LSR siloxanes prescription in the test chart 2.To be used for structurally-modified hydrophobic educt as comparative material.
LSR silicon rubber
In the high speed planetary-type mixer, 20% silica is incorporated in the organopolysiloxane (Silopren U 10 GE Bayer) with low speed (50/500rpm planetary-type mixer/high-speed mixer).In case silica is moistening fully, apply the vacuum of about 200mbar, and under the speed of 100rpm (planetary-type mixer) and 2000rpm (high-speed mixer) (cooling off) with tap water dispersed mixture 30 minutes.After cooling, can crosslinked basic mixture.
Weighing adds 340 gram basic mixtures in the stainless steel beaker.Weighing adds 6.00 gram inhibitor (2% pure ECH in siloxane polymer U 1) and 0.67 gram platinum catalyst solution and 4.19 gram Silopren U 730 in mixture respectively, and the homogenize and the degassing under the speed of n=500rpm.
The sulfuration of prescription
Sulfuration 2mm vulcanized rubber needs the mixture of 4 * 50 grams or 2 * 100 grams.Then under the pressure of 120 ℃ temperature and 100bar in pressing mold extruding sheet rubber 10 minutes.Sulfuration 6mm vulcanized rubber needs 120 gram mixtures.Under the pressure of 120 ℃ temperature and 100bar, in pressing mold, pushed sheet rubber 12 minutes.The postcure vulcanized rubber is 4 hours in 200 ℃ baking oven.
Compare (unmodified on the structure) with comparing silica, the prescription (embodiment 3,7,11) that comprises modified product on the structure demonstrates significantly lower rheological characteristics (table 4).The original value of viscosity ratio use educt is low to reach 60%.
Table 4
Use the rheological characteristics of 20% silica
Silica Yield-point [Pa] Viscosity [Pas] D=10s -1
Embodiment 7 0 54
Embodiment 11 0 55
Embodiment 3 0 51
Compare silica 0 153
Table 5
Use the mechanical characteristic of 20% silica
Silica Tensile strength [N/mm 2] Elongation at break [%] Anti tear is propagated [N/mm] Hardness [Shore A]
Embodiment 7 4.0 300 3.2 41
Embodiment 11 4.1 290 3.4 41
Embodiment 3 5.5 350 23.7 41
Compare silica 5.0 300 4.0 45
Embodiment 3 from table 5 is structurally-modified and subsequently the back grinding and the conditioning of the oxide compound of the preparation of the pyrolysis by the vinyl modification as can be seen, it is propagated to obtain very high anti tear in silicone vulcanizates, and the rheological characteristics of compound also is in low-down level.

Claims (7)

1. the structurally-modified silica of silanization, it is characterized in that being fixed with in its surface vinyl or vinyl silyl, and also additional fastening has the hydrophobic grouping of trimethyl silyl for example and/or dimetylsilyl and/or monomethyl silyl in its surface, and described structurally-modified silica has following physicochemical property:
BET surface-area m 2/ g:25-400
Average primary particle particle diameter nm:5-50
pH： 3-10
Carbon content %:0.1-10
DBP value %:＜200 or detect less than.
2. the method for the structurally-modified silica of the silanization of preparation claim 1 is characterized in that handling silica with surface-modifying agent, the mixture that is obtained is heat-treated structurally-modified then.
3. the method for the structurally-modified silica of the preparation silanization of claim 2 is characterized in that at first water sprays described silica with surface-modifying agent then, and randomly remix is heat-treated then, and carries out structurally-modified subsequently.
4. the method for the structurally-modified silica of the preparation silanization of claim 2 is characterized in that handling described silica with the surface-modifying agent of steam form, described mixture is heat-treated structurally-modified then.
5. the method for the structurally-modified silica of the preparation silanization of claim 3 grinds and/or nurses one's health described structurally-modified silica after it is characterized in that.
6. the method for the structurally-modified silica of the preparation silanization of claim 4 grinds and/or nurses one's health described structurally-modified silica after it is characterized in that.
The structurally-modified silica of the silanization of claim 1 in silicon rubber as the purposes of filler.
CNA2005800070906A 2004-03-05 2005-02-08 Silanised silicas Pending CN1930249A (en)

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